Process for breaking petroleum emulsions



Patented June 7, 1949 UNITED STATES PATENT critics PROCESS FORBREAKING \PET'RLOLEUM EMULSIONS Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware N 6 Drawing. Application March 11, I948, Serial No. 14,397

7* olaims, 01. 252-341) This invention ihtes 101110668568 p e; steari'c ac'id, o1eic acid, and theqike, sd as td'jiilfl dures for preventing, breaking, orres'olviiig emula compound of the forr'nhla:

sions of the Water-imoihtype, 'a'n'd'has for its main -ol'oje'ctto provide anove'l process for resolv- I I i 'ingpetreleuni 'emulsionsof the water in-oil type, 5 NOiHwH' "that a'recommonly referredto'as cut oil, roily Edam;

'0i1,"emulsifie'd oi1,'etc and'Which comprise H 1 fin ropl f fi ilr i yclirr ing waters or The product" of estetified tertiary" ethanole brines dispersediin'" a more" or "less permanent amines" such as the esters 'of' trith-anolamine,

state; throughout the" oil which constitutes the ethyldieth'anolamin e, diethylethafiolaminepetc continuous phase of the'emul's'ion. have 'been' described. "in -the literature; and *pa'rill m er'o je t f r inv nt ni o pr ticularly the"p'atentliteratiirei The-best vide'an economical an'drapid process for sepaexamples a're'th'ose'of the'following' foriniila: rating' emulsionswhich'hav been prepared under controlled conditions from mineral oil, such as 5 crude oil and rel'ativelisoftwaters orweak brin'es. in o 0 OG2H4N/ Controlled 'emlilsificati'on' and subse uent demulsification' 'unfl'erthebonditions just mentioned are of significant value in removing-impfirlties, pa'rin which RC0 is the acyl radical of the higher ti'cularly inorganicsaltsfrom pipeline 'oil'. fatty acid having af'to 22*cai'bon eieins ahuim Demu'lsificati'on, 'a's contemplated in the present and R's-are"selectedirm the elass df alkyi radiapplication; includes the'preventive step of comcells having not more tha1'1 '4 carbon atoms mingling thefdemulsifier-withthe"aqueous com- (methyl, ethyl, propylj-or butyl ethazfol radicals, P 11 'Vii-blah"ll/011111i t subfiequently or ethanol radicals which have been treatd with come either phase ofthe emulsion; in absence of a mole of ethyleneoxide or a mole of glyeide.

S p t y mEQJSHTQ- S rly: such d- If one reacts triethanolamine with 3, 2, or 1 m fiel" y be mixed with thehwdro r m mole of ethylene oxide, the following compounds component. are obtained:

Themateri al, com-pound, product; or-composition ofmatter that is -used-as-t1iederrinlsifying cimocimon oimoczmon czmoomion flq u ga g consistslof'a f 'q NC2HioC2H;O'H mandamus ieamoii polychloride'. uc' 'cation active pt ye ori 'es 2 Y are obtainedbyreaction between an -esterified CZECH monoamirid-al'cohofoi' anest'er'ified monoam'ino Si a H .i, r mllarly, if triethanolamin e is treated with g W and'then treated withf'glyeerolchlorhydt one ethylene glycol bis ichlorofonnatei;the'formula t a. 'for 'suc'h compound beirig-asfollows: then obtains compounds such as the fdlowing.

carbon -atoms,-.for -examp1e, such: astlauricacid;

n. CHzCHr-O-C 0-0.1" olio 40 amoem on'om -ooo -ei elon -Ituis' well knownthat triethanolam-ine can be Actually, however, the usual procedure in forming the esters from tertiary amines such as triethanolamine, is to use the glyceride as a matter of economy. The alcoholysis reaction which takes place may be indicated in the following 4 and carboxy acids produced by the oxidation of petroleum. As will be subseqently indicated, there are other acids which have somewhat similar characteristics and are derived from somewhat different sources, and are different in structure. but can be included in the broad generic term previously indicated.

Among sources of such acids may be mentioned straight chain and branched chain, saturated and unsaturated, carboxylic, aliphatic alicyclic, fatty, aromatic, hydroaromatic, and aralkyl acids The temperature employed for such reaction is generally 175 or somewhat less, in order to avoid etherization of the amino alcohol. Even so, the glycerol liberated from the glyceride may combine with the triethanolamine before acylation takes place. In an event, the fina1 product may be in part an acylated monoamino ether alcohol. Such compound is identical with the one obtained by esterifying or acylating triethanolamine after first treating such an amine with glycide or the equivalent reaction previously described.

Recapitulating what has been said, it is to be noted that the acyl radical may be attached to the nitrogen atom through the radical which contains the ether linkage. Thus, in the broadest aspect, the acylated monoamino alcohols and the acylated monoamino alcohol ethers herein contemplated as a reactant for combination with diglycol chloroformate, may be indicated by the following formula:

R1 ROOOIhN in which RC is the acyl radical of a high molal monocarboxy acid, particularly a higher fatty -acid, and especially, one having 8 to 22 carbon atoms. R1 and R2 are selected from the monovalent radicals.

CH CzHg, C3137, 0411a, C'lHiOH, C2H4O 02 :4011

and R3 is selected from the divalent radicals The expression higher molecular weight carboxy acids is an expression frequently employed to refer to certain organic acids, particularly monocarboxy acids, having more than 6 carbon atoms and generally less than 40 carbon atoms. The commonest examples include the detergent-forming acids, i. e., those acids which combine with alkalies to produce soap or soaplike bodies. The detergent-forming acids, in

turn, include naturally occuring fatty acids, resin acids, such as abietic acid, naturally-occurring petroleum acids such as naphthenic acids,

including caprylic acid, butyric acid, heptylic acid, caproic acid, capric acid, pimelic acid, sebacic acid, erucic acid, saturated and unsaturated higher molecular weight aliphatic acids, such as the higher fatty acids containing at least 8 carbon atoms, and including in addition to those mentioned, melissic acid, stearic acid, oleic acid, ricinoleic acid, diricinoleic acid, triricinoleic acid, polyricinoleic acid, ricinostearolic acid, ricinoleyl lactic acid, acetylricinoleic acid, linoleic acid, linolenic acid, lauric acid, myristic acid, undecylenic acid, palmitic acid, mixtures of any two or more of the above-mentioned acids or other acids, mixed higher fatty acids derived from animal or vegetable sources, for example, lard, cocoanut oil, rapeseed oil, sesame oil, palm kernel oil, palm oil, olive oil, corn oil, cottonseed oil, sardine oil, tallow, soybean oil, peanut oil, castor oil, seal oils, whale oil, shark oil and other fish oils, teaseed oil, partially or completely hydrogenated animal and vegetable oils, such as these mentioned; hydroxy and alphahydroxy higher carboxylic, aliphatic and fatty acids, such as hydroxystearic acid, dihydroxypalmitic acid, dihydroxystearic acid, dihydroxybehenic acid, alphahydroxy capric acid, alphahydroxy stearic acid, alphahydroxy palmitic acid, alphahydroxy lauric acid, alphahydroxy myristic acid, alphahydroxy cocoanut oil mixed fatty acids, alpha.- hydroxy margaric acid, alphahydroxy arachidic acid, and the like; fatty and similar acids derived from various waxes, such as beeswax, spermaceti, montan wax, japan wax, coccerin, and carnauba wax. Such acids include carnaubic acid, cerotic acid, lacceric acid, montanic acid, psyllastearic acid, etc. As suggested, one may also employ higher molecular weight carboxylic acids derived, by oxidation and other methods, from parafiin wax, petroleum and similar hydrocarbons; resinic and hydroaromatic acids, such as hexahydrobenzoic acid, hydrogenated naphthoic hydrogenated carboxydiphenyl, naphthenic, and abietic acid; aralkyl and aromatic acids, such as hexahydrobenzoic acid, hydrogenated naphtheoic, hydrogenated poly-carboxy-diphenyl, naphthenic, and abietic acid; aralkyl and aromatic acids, such as benzoic acid, Twitchell fatty acids, naphthoic acid, carboxy-diphenyl, pyridine carboxylic acid, hydroxybenzoic acid, and the like.

Other suitable acids include phenylstearic acid,

Benzoyincnyiio acid; camphofic" acid}. 'fenchol ic acid,' cetyloxybutyric acid j cety-loxya'cetieacid, etc. Another sou-rec nt suitable acids are those com monly referred' toas' lac acids; such; for example, as the acids derivedufrom.shellac: Such acids include various polyhydroxyfiacids, for example,

I aleuritic acid, shelloic acid,.andlkerrolicnacidh Asiswell .known,.one may usesubs'tituted acids in.whic'h some other non-functional.constituent enters the structure of the fatty acid. For in! stance, one may use aryle, hydroxy-, alk0xy-, keto and amino-derivatives. Generally speaking, however, it is always preferable to use the unsubstituted acid, particularly free from substituentsswhich'icontain' either oxygen or :nitros gen atoms Generally speaking; theintroduc tiom of hydrocarbon radicals,. regardlessi of source;v haslittle effect except in alteringthe hydrophile-hydrophobe "balances I *Gneimay alsoaempl'oy tlie 'blown wcr' oxidized "acids; suchias blown "IiCiIIOI'BiC'3aCid:blDWlIlC O1BiG, or estolides derived from blown oils, such: as blownrcastor oil, blown soyabean-oil, etc.

As previously stated, the-acy1ated inronoamin o 'alll'oholsi' ori' the. 'acyl'ated" monoamino alcohol wethers herein employed as'reactants, arewell known- .compounds and have -'-b een described frequ ently in the literature, particularly the patent literature; Our preieren'ceiis to obtaimthem fromfihigher fatty: acids- 'or' higher fatty acid 'giyceridesand'we particul'arly'prefer to employ ricin'oleic acid, oleicacid; linoleicacid, vlinolenic acid, stearic acid; or the glycerldes which are ai s'ounce: of such fatty acids such as caster oil, neats-foot oil, lard oil, soyabean oil, stearine, 'etc.

We have also found naphthenic acids, .particularly those bearing a molecular weight from "slightly above 200 to slightly less than 400, to be particularly desirable as reactants. We have also employed resin acids such as rosin, abietic acid, etc. Such compounds are obtainable in the manner described and are sometimes obtained conveniently by treating an acylated monoaminoralcohol .o'r a'cylated monoamino alcohol ether with one or two moles of ethylene oxide or glycide.

Such reactants, all of which are well known,

,may, be exemplified by. the following formulae,- in which RC0 is the. acyl radical of a higher fatty acid of the-kind described, orthe acyl radical of the .-.nephthenic acids asdescribed, or the acyl radical of a resin acid such as abietlc acid, etc:

C2H4OH RCOOCaHsOCzHAN H GzExO CeHs(-0H) 2 C'EH4OC3HKOH)! R on 00 311 0 CqHlN H-f Ample (Klkyl -methyl, ethyljpropylfor butyl)" CATION-ACTIVE POLYOHLORIDE Efiramplei" Two gram moles of'themonoricin'oleyi ester of tri'eth'anolamine- (858* grams) is mixedr-with on'e 'gram mole of diglycol chloroformate tfia grams). The mixture was placed in wfiaskwith a suitable stirring device" and "refiux condenser and heated-at .160 tox- C, forone'hour. The mixture showed a.-tendency,to foam when first warmed, but as soon as the reaction started, the ifoaming-tendency-decreased; Themarticm .1an.triethanolamine-zester zemp-loyed'rgavewa; cloudy solution in water. Diglycol chloroformate is, of course, water-insoluble. The resultant product was sufiiciently soluble in water at the end of the reaction period to give a perfectly clear solution and showed a presence of chloride ions.

CATION-ACTIVE POLYCHLORIDE Example 2 The same procedure was followed as in Example 1, preceding, except that two gram moles of the oleic acid ester (826 grams) was employed instead of two gram moles of the ricinoleic acid ester. In all other respects the procedure was identical with that described in Example 1.

CATION-ACTIVE POLYCHLORIDE Ewample 3 The same procedure was followed as in Example 1, preceding, except that two gram moles of the stearic acid ester (830 grams) was employed instead o'ft'wo gram moles-'or the =ri'cino-leicacid ester. In all other respects the precedure 'was identical with that-described in Example 1.

instead of two gram molesof thericinoleic aoid ester. In all other respects the-procedure -was identical with that described in Example 1.

CATION-ACTIVTE POLYCHLORIDE Erramplel. '5-

The same procedure was followed as inlilxample 1; preceding," except that'two .jgramzmolesmf the naphthenic acid ester ('712grams') "was' employed insteadofitwd gram'molesiof the ricinoleio fieidnester. In..all. other .respects the-procedure CATION-ACTIVE POLYCHLORIDE Example 6 The same procedure was followed as in the five preceding examples, except that instead of usin the triethanolamine ester, there was employed the ester of monoethyldiethanolamine. For convenience, the weights employed are indicated by reference to the subsequent table. The table shows the molecular weights of the ester. As in Example 1, the amount employed was two gram moles in each instance.

CATION-ACTIVE POLYCHLORIDE Example 7 The same procedure was followed as in the six preceding examples, except that instead of using the triethanolamine ester, there was employed the ester of For convenience, the weights employed are indicated by reference to the subsequent table. The table shows the molecular weights of the ester. As in Example 1, the amount employed was two gram moles in each instance.

CATION-ACTIVE POLYCHLORIDE Example 8 The same procedure was followed as in the seven preceding examples, except that instead of 8 dicated by reference to the subsequent table. The table shows the molecular weights of the ester. As in Example 1, the amount employed was two gram moles in each instance.

CATION-ACTIVE POLYCHLORIDE Example 10 The same procedure was followed as in the nine preceding examples, except that instead of using 0 the triethanolamine ester, there was employed the ester of )C 2114 O H) z N OzH4OC H(OH)1 For convenience, the weights employed are indicated by reference to the subsequent table. The table shows the molecular weights of the ester. As in Example 1, the amount employed was two gram moles in each instance.

This type of acylated ester can be obtained by a number of procedures, two of which are as follows:

(1) Treat triethanolamine with one mole of glycide and then acylate.

(2) Prepare the acylated ester of triethanolamine and then treat with one mole of glycide. If this procedure is followed, the acyl radical is attached to the ethoxy radical. If the first procedure is followed, one may obtain a mixture of acylated derivatives in which part are characterized by attachment of the acyl radical to the ethoxy radical and part by attachment of the acyl radical to the ether radical.

For convenience, the following table is submitted:

MOLECULAR WEIGHT MONO-ACYL DERIVATIVE I 1 1 0 0 g I 1 a ,2 .2 e m ,I m 0 g m Q g 2 a a g a =3 E .2 o m E a o o 5 0 o Z a 5 E1 2 Q a g a E1 0 s m *5; 1 0 v F-l 6 O '2 v H O a 2 2 Z Z 111 Ricinoleicn 429 413 561 457 651 503 O1elc 413 397 545 441 635 487 Steanc... 415 399 547 443 637 489 Abletlc.. 433 417 565 461 655 507 Naphthemc from Gulf Coast Crude using the triethanolamine ester, there was employed the ester of )CZHOC2H4OH)2 N Ethyl CATION-ACTIVE POLYCHLORIDE Example 9 The same procedure was followed as in the eight preceding examples, except that instead of using the triethanolamine ester, there was employed the ester of For convenience, the weights employed are in- It is obvious that in some instances the hydroxyl available for reaction with the diglycol chloroformate, may be furnished by the acyl radical of the mono-carboxy acid, as in the case of ricinoleic acid, hydroxystearic acid, dihydroxystearic acid, and other hydroxylated acids obtained by the action of hydrogen peroxide on unsaturated fatty acids including undecylenic acid.

In light of what has been said immediately preceding, it is obvious that the amine employed may also include types such as diethylethanolamine, dipropylethanolamine, dibutylethanolamine, and the comparable dialkyl derivatives of glycerylamine. Similarly, an amine of the last mentioned type may be treated with one mole of ethylene oxide prior to acylation, or, inversely, the dialkyl ethanolamines may be treated with a mole of glycide or an equivalent reaction employed prior to acylation.

When prepared from the simplest and most o im readilysavai lablei reactants; i.- e., v5.18 :carboni'fatty I'In practising our .lproce'ss for :resolvirrgip'etroacids and triethanolamine, the structures: *oblemmemulsionsiof the water in oil type, artreattaindare indicatetllbyithe following reaction and ing agent or demulsifying -agent of the kind formula,. assuming' that if the acyl radical has above described is brought-into contact with or an alcoholic hydroxyl, reaction takes place precaused-to act -upo-n -the emulsion to be treated, ferentially at the ethanol'hydroxyl, for the reason in anycoi the various apparatus now generally thatthe-latter is a. primary alcoholic radical and used to resolve or break petroleum emulsions the former is a secondary alcoholic radical. with a chemical reagent, the --above procedure -"onventionaldemulsifyingagents employed in being used either alone orrin.combinationwith the-treatment ofoil fieldemulsions are used as other demulsifying procedure, such as-.;the elec such, or after dilution with any suitable solvent, 2. trical dehydration process.

such as water; petroleum hydrocarbons, such as The demulsifier herein contemplated may be gasoline, kerosene, stove oil; a coal tar product employed in connection with what is commonly such as benzene, toluene, xylene, tar acid oil, known as down-the-hole procedure, i. e., bringcresol, anthracene oil, etc. Alcohols, particularly ing the demulsifier in contact with the fluids of aliphatic alcohols, such as methyl alcohol, ethyl the well at the bottom of the well, or at some alcohol, propyl alcohol, butyl alcohol, hexyl alcopoint prior to emergence of said fluids. This hol, octyl alcohol, etc., may be employed as diluparticular type of application is decidedly feasible ents. Miscellaneous solvents, such as pine oil, when the demulsifier is used in connection with carbon tetrachloride, sulfur dioxide extract obacidification of calcareous oil-bearing strata,

tained in the refining of petroleum, etc., may be 5 especially if suspended in or dissolved in the employed as diluents. Similarly, the material or acid employed for acidification.

materials employed as the demulsifying agent of A somewhat analogous use of our demulsifyour process for resolving emulsions, may be ading agent is in the removal of a residual mud mixed with one or more of the solvents customsheath which remains after drilling a well by arily used in connection with conventional dethe rotary method. Sometimes the drilling mud mulsifying agents. Moreover, said material or contains added calcium carbonate, or the like, to materials may be used alone, or in admixture with render the mud susceptible to reaction with hyother suitable well known cla ses f d l y drochloric acid, or the like, and thus expedite its agents. removal.

It is well known that conventional demulsifying Having thus described our invention, what we agents m y b sed in a water-soluble form, or in claim and desire to secure by Letters Patent is: an oil-soluble form, or in a form exhibiting both 1. A process for breaking petroleum emulsions oil and wa r solub l y- Sometimes t ey y be of the water-in-oil type, characterized by subused in a form which exhibits relatively limited jeeting th emulsion t th ti of a demulsioil solubility. However, since such reagents are fie including a t ti polychloride said sometimes used in a rat o of 1 o 1 1 t0 cation-active polychloride being the reaction even 1 110 even 1 0 1 product of diglycol chloroformate and a hydro- 1 0 50,000111 desalting practice, S an p xylated mono-acylated amine of the following ent insolubility in oil and Water is not significant, formula:

because said reactants undoubtedly have solu- R1 bility within the concentration employed. This RC 0 oRaN/ same fact is true in regard to the material or materials employed as the demulsifying agent of 2 0111 p in which RC0 is the acyl radical of a higher fatty W desire t p t out t t s p ity of acid having at least 8 and not more than 22 carthe r a nt or demu s fy a nt contemplated bon atoms and R1 and R2 are selected from the in 0111 P is based p s a y o treat class consisting of the monovalent radicals certain emulsions more advantageously and at CH8 02H, 03m 04H, CZHOH, CZHOGHOB a somewhat lower cost than is possible with other OH available demulsifiers, or conventional mixtures 13/ thereof. It is believed that the particular decinlocflmooz mulsifying agent or treating agent herein de- OH scribed will find comparatively limited applies" and R3 is selected from the class consisting of tion, so far as the majority of oil field emulsions the divalent radicals are concerned; but we have found that such a C H (N H 00 H C H 00 H demulsifying agent has commercial value, as it 2 1 z will economically break or resolve oil field emul- 0H sions inanumber of cases which cannot be treated it th f rthe proviso that there be at least as s y or at so low a cost with the demulsifying one occurrence of an alcoholic hydroxyl radical agents heretofore available. in the radicals R, R1, R2, and R3.

11 12 2. The process of claim 1, wherein the ratio 7. The process of claim 3, wherein RC0 is a of the hydroxylated mono-acylated amine to linoleyl radical. chloroformate is 2 to 1. MELVIN DE GROOTE. 3. A process for breaking petroleum emulsions BERNHARD KEISER.

of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsi- REFERENCES CITED fier including a cation-active polychloride of the The following references are of record in the following formula: file of this patent:

2000mm CaH4.OOCR I: \n :l

nmmoooommommoc 000,341:

no.0,m cimorr wherein RC0 is the acyl radical of a higher fatty UNITED STATES PATENTS acid having at least 8 and not more than 22 car- Number Name Date bun atoms.

4. The process of claim 3, wherein RC0 is the ggggg 133g fgg gz'iffi i gg fatty 2" 2,231,754 De Groote et a1. Feb. 11, 1941 2,306,329 De Grocte et a1. Dec. 22, 1942 5. The process of claim 3, wherein RCO 1s a 2368 208 Epstein et a1 Jan 30 1945 radlcal 2,373,174 De Groote et 21. M Apr, 10, 1945 6. The process of claim 3, wherein RC0 is an 2 390 078 De Groom et a1 Dec 4 1945 oleyl radical. 25 

